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The guanine functionalization reaction uses singlet oxygen to covalently link single-wall carbon nanotubes to guanine bases in their ssDNA coatings. This creates shallow but densely spaced exciton traps that modulate nanotube band gaps with energetic and spatial control, giving red-shifted electronic transitions. To better understand guanine functionalization, we used quantum chemical computations to compare the stabilities of several candidate addends in multiple orientations on the nanotube surface. Structures of three possible isomers of guanine peroxide (GPO), the reactive intermediate formed through reaction of 9-methyl guanine with singlet O2, were optimized using the semi-empirical PM3 method. To examine effects of nanotube diameter on adduct stability, we then computed the enthalpy changes for bonding of each GPO isomer to a 6 nm segment of (5,4), (6,5), (7,6) and (8,7) SWCNT. Six orientations of the addend on the SWCNT surface were considered for each (n,m) species, giving a total of 72 adduct structures. The results showed that for all four SWCNTs, the most energetically stable adduct is the 4,5-GPO isomer bonded in the ortho L-30 orientation. This adduct can be considered a derivative of 1,4-dioxane. Subsequent ab initio DFT and TDDFT computations comparing bonding orientations of one guanine addend on a 12 nm long SWCNT segment found that ortho L -30 gives a slightly reduced HOMO-LUMO gap, a mildly localized exciton structure, and a slightly red-shifted E11 optical transition as compared to the pristine SWCNT, in agreement with experiment. We conclude that guanine functionalization of near-armchair SWCNTs leads mainly to 4,5-GPO addends bonded in the ortho L -30 orientation.
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This content will become publicly available on January 21, 2026
Complexity in the Photofunctionalization of Single-Wall Carbon Nanotubes with Hypochlorite
The reaction of aqueous suspensions of single-wall carbon nanotubes (SWCNTs) with UV-excited sodium hypochlorite has previously been reported to be an efficient route for doping nanotubes with oxygen atoms. We have investigated how this reaction system is affected by pH level, dissolved O2 content, and radical scavengers and traps. Products were characterized with near-IR fluorescence, Raman, and XPS spectroscopy. The reaction is greatly accelerated by removal of dissolved O2 and strongly suppressed by TEMPO, a radical trap. Alcohols added as radical scavengers alter the reaction efficiency and the product peak emission wavelengths. Photofunctionalization with 300 nm irradiation is substantially less efficient at pH levels low enough to protonate the OCl- ion to HOCl. We deduce that in mildly treated high pH samples, the main product is sp2 hybridized O-doped adducts formed by reaction of SWCNTs with atomic oxygen in its 3P (ground) level. By contrast, treatment under low pH conditions leads to sp3 hybridized SWCNT adducts formed by the addition of secondary radicals from reactions of OH and Cl. There is also evidence for additional photoreactions of product species under stronger irradiation. Researchers using photoexcited hypochlorite for SWCNT functionalization should be alert to the range of products and the sensitivity to reaction conditions in this system.
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- Award ID(s):
- 2203309
- PAR ID:
- 10651348
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- ACS Nano
- Volume:
- 19
- Issue:
- 2
- ISSN:
- 1936-0851
- Page Range / eLocation ID:
- 2497 to 2506
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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